Fungicidal guanidines

ABSTRACT

Guanidines I ##STR1## (A=C 5  -C 12  -cycloalkyl which may bear up to three further substituents; benzyl substituted in the para-position; R 1 , R 2 , R 3  =H, C 1  -C 4  -alkyl; R 4  =C 5  -C 18  -alkyl which may be interrupted by oxygen, C 5  -C 18  -alkenyl, C 4  -C 18  -alkynyl or phenyl-C 1  -C 6  -alkyl, and these groups may bear up to three further substituents and the phenyl moiety of the phenylalkyl may additionally bear a phenoxy group or up to three C 2  -C 4  -alkenyl, C 1  -C 4  -alkoxy-C 1  -C 4  -alkyl, C 1  -C 6  -alkyl or haloalkyl groups, C 5  -C 6  -cycloalkyl-C 1  -C 8  -alkyl, where the ring may bear up to three further substituents; A=benzyl and R 4  =C 3  -C 4  -alkyl which may be interrupted by oxygen, or C 4  -alkenyl, both of which may bear up to three further substituents; R 3  +R 4  =C 5  -C 6  -heterocycle which may bear up to three further substituents and may be interrupted by oxygen) 
     and the salts I.HX and the metal complexes of I. 
     The compounds I are suitable as fungicides.

This is a divisional of application Ser. No. 547,194, filed Jul. 3, 1990now U.S. Pat. No. 5,126,374.

The present invention relates to novel guanidines of the formula I##STR2## where A is cycloalkyl which has 5 to 12 carbon atoms in thering and may carry up to three of the following substituents: hydroxyl,halogen, C₁ -C₁₀ -alkyl, C₁ -C₁₀ -alkoxy, C₁ -C₁₀ -haloalkyl and C₁ -C₈-alkoxy-C₁ -C₈ -alkyl; or benzyl which is substituted in the paraposition by C₁ -C₁₀ -alkyl or C₁ -C₁₀ -alkoxy, where the substituent mayfurthermore carry a hydroxyl or a C₁ -C₆ -alkoxy group;

R¹, R² and R³ are each hydrogen or C₁ -C₄ -alkyl, and

R⁴ is C₅ -C₁₈ -alkyl which may be interrupted by oxygen, or is a C₅ -C₁₈-alkenyl group, a C₄ -C₁₈ -alkynyl group or a phenyl-C₁ -C₆ -alkylgroup, where these groups may carry up to three of the followingsubstituents: hydroxyl, halogen, cyano, C₁ -C₇ -alkoxy or up to twoamino, C₁ -C₄ -alkylamino or di-(C₁ -C₄)-alkylamino substituents and thephenyl moiety of the phenylalkyl group may additionally carry a phenoxygroup or up to three C₂ -C₄ -alkenyl groups, C₁ -C₄ -alkoxy-C₁ -C₄-alkyl groups or C₁ -C₆ -alkyl groups which may be unsubstituted orpartially or completely halogenated, or C₅ - or C₆ -cycloalkyl-C₁ -C₈-alkyl where the cycloalkyl ring may carry up to three C₁ -C₄ -alkylgroups or up to two hydroxyl or trifluoromethyl groups; or, where A is abenzyl group according to the definition, C₃ - or C₄ -alkyl which may beinterrupted by oxygen or may carry a C₄ -alkenyl group, where thesegroups may carry up to three of the following substituents: hydroxyl,halogen, cyano, C₁ -C₇ -alkoxy or up to two amino, C₁ -C₄ -alkylamino orC₂ -C₈ -dialkylamino groups; or, together with the radical R³ and thenitrogen atom, may form a 5-membered or 6-membered heretocyclic ringwhich may be monosubstituted to trisubstituted by C₁ -C₆ -alkyl, phenylor C₁ -C₆ -alkylphenyl or may be interrupted by an oxygen atom,

and the plant-tolerated mineral acid salts I.HX and metal complexes ofI.

The present invention furthermore relates to processes for thepreparation of these compounds, their use as fungicides, and fungicideswhich contain these compounds as active substances.

The monograph Chemie der Pflanzenschutz- undSchadlingsbekampfungsmittel, Volume 4, Springer Verlag 1977, page 145 etseq., discloses fungicidal alkylguanidine salts (dodines) andbisalkylguanidineamine salts (guazatines) which carry an alkyl group onone of the guanidine nitrogen atoms or whose guanidino groups are linkedto one another by an azaalkylene group.

Guanidine derivatives which have a fungicidal action and arearyl-substituted at one nitrogen atom and substituted by alkyl andcycloalkyl groups at the two other nitrogen atoms are described inDE-A1-31 08 564.

However, the actions of these compounds may be satisfactory only undercertain circumstances, particularly in the case of low application ratesand concentrations. In particular, some of them cause damage to crops.

It is an object of the present invention to provide novel fungicidalcompounds which, even at relatively low application rates, have betterfungicidal properties than the compounds known to date, without causingsignificant damage to the crops.

We have found that this object is achieved by the guanidines of theformula I which were defined at the outset. We have also found processesfor the preparation of these guanidines.

If R¹ and/or R³ are hydrogen, the compounds I may furthermore be presentin tautomeric forms, which are described by formula I.

The substituents in the novel compounds I have the following specificmeanings:

A is cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl or cyclododecyl,where these groups may carry up to three of the following radicals:

hydroxyl;

halogen, including in particular fluorine;

straight-chain or branched C₁ -C₁₀ -alkyl, in particular C₁ -C₆ -alkyl,such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, 1,1-dimethylpropyl or 2,4,4-trimethylpent-2-yl;straight-chain or branched C₁ -C₁₀ -alkoxy, in particular C₁ -C₆-alkoxy, such as methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy oroctyloxy; straight-chain or branched, partially or completelyhalogenated C₁ -C₁₀ -haloalkyl, in particular C₁ -C₆ -haloalkyl, such astrifluoromethyl or pentafluoroethyl;

C₁ -C₈ -alkoxy-C₁ -C₈ -alkyl, in particular C₁ -C₄ -alkoxy-C₁ -C₄-alkyl, such as methoxymethyl, ethoxymethyl, methoxyethyl,tert-butoxymethyl or 1-methoxy-1-methylethyl; or

benzyl which may carry one of the following substituents in the paraposition:

straight-chain or branched C₁ -C₁₀ -alkyl, in particular C₁ -C₆ -alkyl,such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl,tert-butyl, 1,1-dimethylethyl, 1,1-dimethylpropyl, 2,3-dimethylpropyl,1,1,2-trimethylpropyl, 2-hydroxyprop-2-yl or 2-methoxyprop-2-yl;

C₁ -C₁₀ -alkoxy, in particular C₁ -C₆ -alkoxy, such as methoxy, ethoxy,isopropoxy, n-butoxy, tert-butoxy or hexyloxy;

particularly preferred radicals A are cyclopentyl, cyclohexyl,cycloheptyl, 1-methoxy-1-methylethylcyclohexyl, 2-methylcyclohexyl,3-methylcyclohexyl, 3-trifluoromethylcyclohexyl, 3,3-dimethylcyclohexyl,3,3,5-trimethylcyclohexyl, 4-hydroxycyclohexyl, 4-chlorocyclohexyl,4-chloroethylcyclohexyl, 4-isopropylcyclohexyl,4-(1-methoxyisopropyl-cyclohexyl, 4-tert-butylcyclohexyl,4-(1,1-dimethylpropyl)-cyclohexyl, 4-ethoxycyclohexyl,4-tert-butoxycyclohexyl, 4-(2,4,4-trimethylhex-2-yl)-cyclohexyl, benzyl,p-methylbenzyl, p-ethylbenzyl, p-isopropylbenzyl, p-tert-butylbenzyl,p-(2,3-dimethylpropyl)-benzyl, p-(1,1-dimethylethyl)-benzyl,p-(1,1,2-trimethylpropyl)benzyl, p-(2-hydroxyprop-2-yl)-benzyl,p-(2-methoxyprop-2-yl)-benzyl, p-methoxybenzyl or p-tert-butoxybenzyl;

R¹, R² and R³ are each preferably hydrogen, methyl, ethyl, propyl,isopropyl, n-butyl or isobutyl;

R⁴ is straight-chain or branched C₅ -C₁₈ -alkyl which may be interruptedby oxygen, preferably 2,2-dimethylpropyl, 3-methylbutyl,3,3-dimethylbutyl, n-pentyl, 4,4-dimethylpentyl, n-hexyl, 2-ethylhexyl,3,5,5-trimethylhexyl, n-heptyl, n-octyl, 5-methyloct-2-yl,2-hydroxyoctyl, 8-hydroxyoctyl, 8-fluorooctyl, 8-chlorooctyl,2,5,7,7-tetramethyloctyl, n-nonyl, n-decyl, n-dodecyl, n-tri-decyl,isotridecyl, 6,10-dimethylundec-2-yl, 6,10,14-trimethylpentadec-2-yl,n-hexadecyl, n-octadecyl, 4-(4-tert-butoxy)-but-2-yl, tert-butoxypentyl,6-ethyl-4-oxadecyl or 3-diethylaminopropyl;

straight-chain or branched C₅ -C₁₈ -alkenyl or C₄ -C₁₈ -alkynyl, inparticular dimethylallyl or but-2-ynyl; phenyl-C₁ -C₆ -alkyl, inparticular phenyl-C₁ -C₄ -alkyl, which may carry a phenoxy group or upto three of the following radicals:

hydroxyl;

halogen, including in particular fluorine or

chlorine;

cyano; straight-chain or branched C₁ -C₇ -alkoxy, in particular C₁ -C₄-alkoxy, such as methoxy, ethoxy, isopropoxy, n-butoxy or tert-butoxy,or up to 2 amino, C₁ -C₄ -alkylamino and/or di-C₁ -C₄ -alkylaminosubstituents, in particular amino, dimethylamino and diethylamino;

phenoxy on the phenyl moiety of the phenylalkyl group;

up to three of the following substituents on the phenyl moiety of thephenylalkyl group:

straight-chain or branched C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, in particularC₁ -C₄ -alkoxy-C₁ - or -C₂ -alkyl, such as methoxymethyl, ethoxymethylor ethoxyethyl; straight-chain or branched C₂ -C₄ -alkenyl, inparticular ethenyl or isopropenyl; C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl, such asmethoxymethyl, or straight-chain or branched C₁ -C₆ -alkyl or partiallyor completely halogenated C₁ -C₆ -haloalkyl, in particular methyl,trichloromethyl, trifluoromethyl, ethyl, propyl, isopropyl, n-butyl,tert-butyl, 1,1-dimethylpropyl, 1,1,2-trimethylpropyl,2,4,4-trimethylpentyl or perfluoropentyl;

particularly preferred radicals are benzyl, 4-hydroxybenzyl,3-chlorobenzyl, 4-chlorobenzyl, 2,4-dichlorobenzyl, 4-cyanobenzyl,4-methylbenzyl, 4-trifluoromethylbenzyl, 4-trichloromethylbenzyl,4-isopropylbenzyl, 4-isopropenylbenzyl, 3-tert-butylbenzyl,4-tert-butylbenzyl, 4-(1,1-dimethylpropyl)-benzyl,4-(1,1,2-trimethylpropyl)-benzyl, 4-(2,4,4-trimethylpentyl)-benzyl,4-(1-hydroxy-1-methylethyl)-benzyl, 3,5-di-tert-butyl-4-hydroxybenzyl,4-methoxybenzyl, 4-(1-methoxy-1-methylethyl)-benzyl, 4-n-butoxybenzyl or4-tert-butoxybenzyl, 1-phenylethyl, phenethyl, 4-methoxyphenethyl,4-tert-butylphenethyl, 3-phenylpropyl,3-(4-tert-butylphenyl)2-methylpropyl or 4-phenylbut-2-yl;

a C₅ - or C₆ -cycloalkyl-C₁ -C₈ -alkyl group where the cycloalkyl ringmay carry up to three C₁ -C₄ -alkyl groups, such as methyl ortert-butyl, or up to two hydroxyl or trifluoromethyl groups, inparticular a C₅ - or C₆ -cycloalkyl-C₁ -C₄ -alkyl group, such ascyclohexylmethyl, 4-tert-butyl-cyclohexylmethyl,4-trifluoromethylcyclohexylmethyl, 4-hydroxycyclohexylmethyl,4-tert-butoxycyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl or3-(4-tert-butylcyclohexyl)-2-methylpropyl;

or, where A is a benzyl group according to the definition,

straight-chain or branched C₃ - or C₄ -alkyl which may be interrupted byoxygen, in particular isopropyl, tert-butyl or 2-hydroxypropyl; or C₄-alkylene, in particular but-2-enyl;

or, together with R³ and the nitrogen atom, is a 5-membered or6-membered heterocyclic structure which may be monosubstituted totrisubstituted by C₁ -C₆ -alkyl, phenyl or C₁ -C₆ -alkylphenyl and maybe interrupted by an oxygen atom; in particular2-(1,5-dimethylhexyl)-pyrrolidinyl,2-(2,4,4-trimethylpentyl)-pyrrolidinyl, 3-phenylpyrrolidinyl,3-(4-tert-butylphenyl)-pyrrolidinyl,3-(4-tert-butylphenyl)-4-methylpyrrolidinyl, piperidinyl,4-tert-butylpiperidinyl, 4-(4-tert-butylphenyl)-piperidinyl, morpholinylor 2,6-dimethylmorpholin-4-yl.

Particularly suitable compounds I are shown in the Table, those whichcarry the following substituents being particularly preferred:

A is cyclohexyl, 3,3-dimethylcyclohexyl, 4-tert-butylcyclohexyl orp-tert-butylbenzyl;

R¹ is hydrogen;

R² is hydrogen or C₁ -C₄ -alkyl;

R³ is hydrogen or methyl; and

R⁴ is C₆ -C₁₄ -alkyl, in particular 2-ethylhexyl or6,10-dimethylundec-2-yl, or

p-(C₁ -C₆ -alkyl)-phenyl-C₁ -C₄ -alkyl, in particularp-tert-butylbenzyl, 3-(p-tert-butylphenyl)-2-methylpropyl orp-(2,3-dimethylbut-2-yl)-benzyl, or together with R³ and the nitrogenatom, forms 4-tertbutylphenylpyrrolidinyl.

Suitable acid addition salts are the plant-tolerated salts of acidswhich do not adversely affect the fungicidal action of I, for examplethe iodides, chlorides, bromides, hydrochlorides, hydrobromides,sulfates, dodecylsulfates, nitrates, carbonates, phosphates, formates,acetates, propionates, benzoates, oxalates, naphthalenesulfonates,dodecylbenzenesulfonates, lactates and the salts with the anion ofsaccharin. The iodides, chlorides and acetates are preferred.

Suitable metal complexes are the complexes of copper, of zinc, of tin,of manganese, of iron, of cobalt or of nickel. The complexes arepreferably prepared from the free bases I and salts of mineral acids,for example the chlorides or sulfates, with the metals.

The following compounds I are very particularly suitable:

N-1-cyclohexyl-N-2-(6,10-dimethylundec-2-yl)-guanidine hydriodide,

N-1-cyclohexyl-N-2-[3-(p-tert-butylphenyl)-2-methylpropyl]-quanidinehydriodide,

N-1-(2,2-dimethylcyclohexyl)-N-2-[3-(p-tert-butylphenyl)-2-methylpropyl]-guanidinehydriodide,

N-1-cyclohexyl-N-2-(p-tert-butylbenzyl)-guanidine hydrochloride,

N-1-(3,3-dimethylcyclohexyl)-N-2-(p-tert-butylbenzyl)-guanidinehydrochloride,

N-1-cyclohexyl-N-2-[p-(2,3-dimethylbut-2-yl)-benzyl]-guanidinehydriodide,

N-1-(p-tert-butylcyclohexyl)-N-2-(p-tert-butylbenzyl)-N-3-methylguanidinehydriodide,

N-1-cyclohexyl-N-2-n-butyl-N-3-(p-tert-butylbenzyl)-guanidinehydroacetate,

N-1-cyclohexyl-N-2-(p-tert-butylbenzyl)-N-2-methylguanidinehydroacetate,

N-1-(p-tert-butylbenzyl)-N-2-(2-ethylhexyl)-guanidine hydriodide,

N-1-(p-tert-butylbenzyl)-N-2-(p-tert-butylbenzyl)-N-3-methylguanidinehydriodide and

1-{[(3,3-dimethylcyclohexyl)-amino]-iminomethyl}-[3-(p-tert-butylphenyl)]-pyrrolidine.

The guanidines I are obtainable in various ways, preferably by thefollowing methods:

a) Preparation from thiuronium salts and amines ##STR3##

In these formulae, R⁵ is benzyl or a short-chain alkyl radical, e.g.methyl or ethyl, and X' is advantageously chloride, bromide, iodide,sulfate, methylsulfate, methylsulfonate or tosylate.

The starting compounds IIa-IIc and IIIa-IIIc are known or are obtainablein a known manner; regarding the thiuronium salts, reference may be madeto Houben-Weyl, Methoden der Organischen Chemie, 4th edition, Vol. IX,page 900 et seq.

The reaction, known per se from Houben-Weyl, Methoden der OrganischenChemie, 4th edition, Vol. VIII, page 1893 et seq. and Vol. E4, page 614et seq., of thiuronium salts with amines to give the quanidinederivatives I·HX' is preferably carried out in polar solvents such asalcohols, ketones, ethers, nitriles, dimethyl sulfoxide,N-methylpyrrolidone, dimethylformamide or dimethylacetamide.

The ratios of the reactants may be varied depending on the compoundsused. Advantageously, equimolar amounts are reacted or, particularlypreferably, twice the required amount of the amine component is used.Furthermore, a tertiary amine, such as triethylamine, may also be addedas an auxiliary base to trap the mercaptan being formed. In this case,equimolar amounts, based on the thiuronium salt, of the auxiliary baseare preferably used.

It is advisable to carry out the reactions at from 20° C. to the boilingpoint of the solvent, preferably from 60° to 130° C. Since the reactionsare not pressure-dependent, they are preferably carried out underatmospheric pressure.

By anion exchange, it is possible to obtain salts with other anionsX.sup.⊖ or, in the case of exchange with hydroxyl ions, the free basesI.

b) Preparation from aminoiminomethanesulfonic acids and amines ##STR4##

The starting compounds IVa-IVd are known or are obtainable in a knownmanner from thiourea derivatives (e.g. C. A. Maryanoff et al., J. Org.Chem. 51 (1986), 1882 et seq.).

The reaction, known per se from C. A. Maryanoff et al., loc. cit., ofaminoiminosulfonic acids with amines to give the guanidine derivatives Iis preferably carried out in a polar solvent, such as an alcohol or,particularly preferably, in acetonitrile.

It is advisable to carry out the reactions at from 0° C. to the boilingpoint of the solvent.

Regarding the ratios and the pressure, the data for Method a) areapplicable.

c) Preparation from carbodiimides and amines ##STR5##

The starting compounds Va-Vc are known or are obtainable by knownprocesses. By way of example, reference may be made to M. Mikolaiczyk,Tetrahedron 37 (1981), 233 et seq., Z. M. Jaaszay et al., Synthesis,1987, 520 et seq., and G. Appel et al., Chem. Ber. 104 (1971), 1335 etseq.

The reaction, known per se from Houben-Weyl, Methoden der OrganischenChemie, 4th edition, Vol. VIII, page 180 and Vol. E4, page 609, ofcarbodiimides with amines to give the guanidine derivatives I ispreferably carried out in a nonpolar solvent, such as hexane, toluene, ashort-chain alcohol, such as methanol or isopropanol, or a nitrile, suchas acetonitrile.

For the reactions, it is advisable to use equimolar amounts of thestarting compounds or, preferably, a small excess of the aminecomponent, i.e. not more than about 10%.

Regarding the temperature and the pressure, the data for Method a) areapplicable.

d) Preparation from diphenylimidocarbonates and amines ##STR6## Informula IVa, R⁶ is cyano, benzoyl or methanesulfonyl.

The reaction, known per se from A. Buschauer, Arzneim.-Forsch./Drug Res.37 (II) (1987), 1003/1008 et seq., and Arch. Pharm. 321 (1988), 281, ofdiphenylimidodicarbonates with two amines is carried out in two separatestages. The reaction of the imidocarbonate with the first amine ispreferably effected in a chlorohydrocarbon, such as methylene chloride,in ether, such as tetrahydrofuran or diethyl ether, or a nitrile, suchas acetonitrile. The further reaction of the product with the secondamine is carried out in a polar solvent, such as acetonitrile orpyridine.

Regarding the ratios, the temperature and the pressure, the data forMethod c) are applicable.

The hydrolysis of the resulting bases I where R² =R⁶ is carried out in aknown manner, advantageously in a mineral acid at, for example, from 70°to 120° C. Preferably, 2-12.5M hydrochloric acid is used under reflux.

The chloride salts of the novel compounds I in which R² is hydrogen areobtained.

e) Preparation from cyanogen bromide and amines ##STR7## In theseformulae, X" is preferably chloride.

The reaction, known per se from H. W. Geluk et al., J. Med. Chem. 12(1969), 712 et seq., of cyanogen bromide with amines to giveN-substituted cyanamide derivatives VIIa or VIIb is preferably carriedout in an ether, such as diethyl ether or tetrahydrofuran.

An excess of the amine component over the cyanogen bromide, i.e. notmore than about 60%, is advantageously used.

It is advisable to carry out the reaction at from 0° to 25° C. Since thereactions are not pressuredependent, they are preferably effected underatmospheric pressure.

The reaction of the N-substituted cyanamides VIIa and VIIb with thehydrochlorides of the amines IIIb and IIIa is preferably carried out inthe absence of a solvent, at, for example, from 150° to 250° C.

Regarding the amounts used, the pressure or the preparation of the freebases I, the data for Method c) are applicable.

The compounds of the formula I and their salts and metal complexesaccording to the definition are suitable as fungicides and are welltolerated by plants.

Generally speaking, the guanidines according to the invention areextremely effective on a broad spectrum of phytopathogenic fungi, inparticular those from the Ascomycetes and Basidiomycetes classes. Someof them have a systemic action and can be used as foliar and soilfungicides.

The fungicidal compounds are of particular interest for controlling alarge number of fungi in various crops or their seeds, especially wheat,rye, barley, oats, rice, Indian corn, lawns, cotton, soybeans, coffee,sugar cane, fruit and ornamentals in horticulture and viticulture, andin vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling thefollowing plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia species in cotton and lawns,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Helminthosporium species in cereals,

Septoria nodorum in wheat,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercospora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Phytophthora infestans in potatoes and tomatoes,

Fusarium and Verticillium species in various plants,

Plasmopara viticola in grapes,

Alternaria species in vegetables and fruit.

The guanidines I are particularly suitable for combating Botrytiscinerea.

The compounds are applied by treating the plants, or the seed, materialsor soil to be protected against fungus attack with a fungicidallyeffective amount of the active ingredients.

The novel substances can be converted into conventional formulationssuch as solutions, emulsions, suspensions, dusts, powders, pastes andgranules. The application forms depend entirely on the purposes forwhich they are intended; they should at all events ensure a fine anduniform distribution of the active ingredient. The formulations areproduced in known manner, for example by extending the active ingredientwith solvents and/or carriers, with or without the use of emulsifiersand dispersants; if water is used as solvent, it is also possible toemploy other organic solvents as auxiliary solvents. Suitableauxiliaries for this purpose are solvents such as aromatics (e.g.,xylene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g.,crude oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g.,cyclohexanone), amines (e.g., ethanolamine, dimethylformamide), andwater; carriers such as ground natural minerals (e.g., kaolins,aluminas, talc and chalk) and ground synthetic minerals (e.g., highlydisperse silica and silicates); emulsifiers such as nonionic and anionicemulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and aryl sulfonates); and dispersants such as lignin-sulfitewaste liquors and methylcellulose.

The fungicidal agents generally contain from 0.1 to 95, and preferablyfrom 0.5 to 90, wt % of active ingredient. The application rates arefrom 0.01 to 6, and especially from 0.02 to 3, kg of active ingredientper hectare, depending on the type of effect desired. The novelcompounds may also be used for protecting materials (wood), for exampleagainst Paecilomyces variotii.

When the active ingredients are used for treating seed, amounts of from0.001 to 50, and preferably from 0.01 to 10, g per kg of seed areusually employed.

The agents and the ready-to-use formulations prepared from them, such assolutions, emulsions, suspensions, powders, dusts, pastes and granules,are applied in conventional manner, for example by spraying, atomizing,dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. A solution of 90 parts by weight of compound no. 3a and 10 parts byweight of N-methyl-α-pyrrolidone, which is suitable for application inthe form of very fine drops.

II. A mixture of 20 parts by weight of compound no. 2a, 80 parts byweight of xylene, 10 parts by weight of the adduct of 8 to 10 moles ofethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts byweight of the calcium salt of dodecylbenesulfonic acid, and 5 parts byweight of the adduct of 40 moles of ethylene oxide and 1 mole of castoroil; by finely distributing the solution in water a dispersion isobtained.

III. An aqueous dispersion of 20 parts by weight of compound no. 5a, 40parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20parts by weight of the adduct of 40 moles of ethylene oxide and 1 moleof castor oil.

IV. An aqueous dispersion of 20 parts by weight of compound no. 26a, 25parts by weight of cyclohexanol, 65 parts by weight of a mineral oilfraction having a boiling point between 210° and 280° C., and 10 partsby weight of the adduct of 40 moles of ethylene oxide and 1 mole ofcastor oil.

V. A mixture, triturated in a hammer mill, of 80 parts by weight ofcompound no. 37a, 3 parts by weight of the sodium salt ofdiisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of the sodiumsalt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and7 parts by weight of powdered silica gel; by finely distributing themixture in water, a spray liquor is obtained.

VI. An intimate mixture of 3 parts by weight of compound no. 1b and 97parts by weight of particulate kaolin. This dust contains 3% by weightof the active ingredient.

VII. An intimate mixture of 30 parts by weight of compound no. 2b, 92parts by weight of powdered silica gel and 8 parts by weight of paraffinoil sprayed onto the surface of this silica gel; this formulation of theactive ingredient has good adherence.

VIII. A stable aqueous dispersion of 40 parts by weight of compound no.4b, 10 parts by weight of the sodium salt of a phenolsulfonicacid-ureaformaldehyde condensate, 2 parts of silica gel and 48 parts ofwater; this dispersion can be further diluted.

IX. A stable oily dispersion of 20 parts by weight of compound no. 9b, 2parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8parts by weight of a fatty alcohol polyglycol ether, 2 parts by weightof the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensateand 68 parts by weight of a paraffinic mineral oil.

In these application forms, the agents according to the invention mayalso be present together with other active ingredients, for exampleherbicides, insecticides, growth regulators, and fungicides, and mayfurthermore be mixed and applied together with fertilizers. Admixturewith other fungicides frequently results in an increase in thefungicidal spectrum.

MANUFACTURING EXAMPLES Example A, according to method a) (compound 7b intable)N-1-(4-tert.-butylbenzyl)-N-2-methyl-N-3-(3,5,5-trimethyl-hexyl)-guanidinehydroiodide ##STR8##

Under a nitrogen blanket, a mixture of 19 g (0.05 mol) ofN-(4-tert.-butylbenzyl)-N',S-dimethylisothiuronium iodide, 14.1 g (0.1mol) of 3,5,5-trimethylhexylamine, 5 g (0.05 mol) of triethylamine and20 g of molecular sieve (4 Å) in 200 ml of anhydrous acetonitrile wasrefluxed for 6 hours with elimination of methanethiol. After filtrationwhile hot, the mixture was worked up in the usual manner.

Yield: 64% of theroy; m.p. 165° C.

Intermediate stage A1 N-(4-tert.-Butylbenzyl)-N'-methylthiourea ##STR9##

At 20° to 30° C., a solution of 163 g (1 mol) of4-tert.-butylbenzylamine in 100 ml of anhydrous acetonitrile wasdripped, while cooling, into a mixture of 73 g (1 mol) of methylisothiocyanate in 80 ml of anhydrous acetonitrile. The mixture wasstirred for 3 hours at 20° C. and then for a further hour at 80° to 90°C. before being evaporated down. The crude product was precipitated withhexane from ethyl acetate, washed with hexane and dried under reducedpressure at 60° C.

Yield: 72% of theory; mp 72° C.

Intermediate stage A2 N-(4-tert-Butylbenzyl)-N',S-dimethylisothiuroniumiodide ##STR10##

A solution of 23.6 g (0.1 mol) ofN-(4-tert.-butylbenzyl)-N'-methylthiourea and 114.2 g (0.1 mol) ofiodomethane in 200 ml of methanol was refluxed for one hour. After themixture had cooled to room temperature the product was precipitated byadding methyl tert-butyl ether, washed and dried under reduced pressureat 40° C.

Yield: 53% of theory; mp: 172° C.

Example B, according to method a) (compound 20b in table)N-1-(4-tert.-Butylbenzyl)-N-2-n-octylguanidin hydroiodide ##STR11##

A mixture of 9.1 g (2,5.10⁻² mol) ofN-(4-tert.-butylbenzyl)-S-methylisothiuronium iodide, 6.5 g (5.10⁻² mol)of n-octylamine, 2.5 g (25 mmol) of triethylamine, 3 g of molecularsieve (4 Å) and 200 ml of acetonitrile was refluxed for 48 hours andworked up as described in Example A.

Yield: 61% of theory; mp.: 113° C.

Intermediate stage B1 N-(4-tert.-Butylbenzyl)-thiourea ##STR12##

Over a period of 10 minutes, a solution of 147.5 g (1.05 mol) of benzoylchloride was dripped into a solution of 82.5 g (1.1 mol) of ammoniumthiocyanate in 300 ml of absolute acetone. After the mixture had beenstirred for 10 minutes at the reflux temperature, a solution of 163 g (1mol) of 4-tert.-butylbenzylamine in 150 ml of acetone was dripped in,and the reaction mixture was refluxed for 20 minutes and stirred into 2liters of ice water. The precipitated solid was washed with water,dissolved in a hot mixture of 1 liter of 10% strength caustic solutionand 550 ml of ethanol and refluxed for a further 15 minutes.

The mixture was then diluted with ice water, adjusted with concentratedhydrochloric acid to a pH of 1 and then with solid sodium bicarbonate toa pH of about 9. The resulting precipitate was washed with water anddried under reduced pressure at 60° C.

Yield: 92% of theory; mp.: 80° C.

Intermediate stage B2 N-(4-tert.-Butylbenzyl)-S-methylisothiuroniumiodide ##STR13##

At 30° to 40° C., 54.4 g (0.333 mol) of iodomethane was dripped into 85g (0.383 mol) of N-(4-tert.-butylbenzyl)-thiourea in 200 ml of methanol.The mixture was reacted and worked up analogously to Example A,intermediate stage A2; the product was dried at 60° C.

Yield: 74% of theory; mp.: 143° C.

Example C, according to method a) (example 1a in table)N-1-Cyclohexyl-N-2-(4-tert.-butylbenzyl)-guanidine hydroiodide ##STR14##

30 g (0.1 mol) of N-cyclohexyl-S-methylisothiuronium iodide, 32.6 g (0.2mol) of 4-tert.-butylbenzylamine, 10.1 g (0.1 mol) of triethylamine and3 g of molecular sieve (4 Å) were reacted for 48 hours in 200 ml ofanhydrous acetonitrile analogously to Example A.

Yield: 95% of theory; mp.: 145°-150° C.

Example D, according to method a) (example 41a in table)N-1-(3-methyl-cyclohexyl)-N-2-(4-tert.-butylbenzyl)-N-3-methylguanidinehydroiodide ##STR15##

9.5 g (25 mmol) of N-(4-tert.-butylbenzyl)-N', S-dimethylisothiuroniumiodide, 5.7 g (50 mmol) of 3-methylcyclohexylamine (isomer mixture), 2.5g (25 mmol) of triethylamine and 1.5 g of molecular sieve (4 Å) in 100ml of acetonitrile were reacted for 2 hours analogously to Example A.

Yield: 25% of theory; mp.: 150° C.

Example E, according to method c) (example 11b in table)N-1-(4-tert.-Butylbenzyl)-N-2-n-butyl-N-3-(2,2-dimethylpropyl)-quanidinehydrochloride ##STR16##

A mixture of 2 g (8,2.10⁻³ mol) ofN-(4-tert.-butylbenzyl)-N'-n-butyl-carbodiimide, 0.17 g (8,2.10⁻³ mol)of 2,2-dimethylpropylamine and 100 ml of anhydrous tert.-butanol wasrefluxed for 24 hours. An oily product was isolated, methanolichydrochloric acid was added, and the mixture was concentrated underreduced pressure and crystallized by trituration with methyl tert.-butylether.

Yield: 33% of theory; mp.: 88° C.

Example F, according to method c) (example 57a in table)N-1-(4-tert.-butyl-cyclohexyl)-N-2-n-butyl-N-3-(4-tert.-butylbenyl)-guanidinhydrochloride ##STR17##

2 g (8,2.10⁻³ mol) of N-(4-tert.-butylbenzyl)-N'-n-butylcarbodiimide and1.27 g (8,2.10⁻³ mol) of 4-tert.-butylcyclohexylamine were reactedanalogously to Example E.

Yield: 30% of theory; mp.: 110° C.

Example G (example 30a in table)N-1-cyclohexyl-N-2-[3-(4-tert.-butylphenyl)-2-methylpropyl]-guanidinehydrochloride ##STR18##

21.8 g (6,6.10⁻² mol) ofN-1-cyclohexyl-N-2-[3-(4-tert.-butylphenyl)-2-methylpropyl]-guanidinehydroiodide (example 26a from Table 1) in 300 ml of methanol/water (1:1)were filtered through a column containing 250 g of Amberlyst A 26(OH.sup.⊖ form). After working up, the free guanidine obtained wasconverted into the hydrochloride with an excess of methanolichydrochloric acid.

Yield: 80%; mp.: 169° C.

The compounds listed in Table 1 below were obtained analogously toExamples A to G:

                                      TABLE 1                                     __________________________________________________________________________     ##STR19##                                                                    Comp.                                                                         No.  A        R.sup.1                                                                           R.sup.2                                                                            R.sup.3                                                                          R.sup.4       HX      mp./IR (film) [cm.sup.-1      __________________________________________________________________________                                                    ]                              1a  cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         HI      145° C.                 2a  cyclohexyl                                                                             H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      180° C.                 3a  cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         HI      140° C.                 4a  cyclohexyl                                                                             CH.sub.3                                                                          H    H  4-tert.-butylbenzyl                                                                         HI      152° C.                 5a  cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         HCl     195° C.                 6a  cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         195° C.                 7a  cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         (COOH).sub.2                                                                          1719, 1703, 1615, 1515,                                                       1445, 1403, 1230, 1202,                                                       1173, 721                      8a  cyclohexyl                                                                             H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         2930, 2854, 1586, 1514,                                                       1463, 1450, 1393, 1364         9a  cyclohexyl                                                                             H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HCl     3253, 3200, 3102, 2932,                                                       2856, 1625, 1451, 1366,                                                       1347, 1174                     10a cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         --      2936, 1652, 1606, 1487,                                                       1398, 1094, 1072, 1007         11a cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         HCl     140° C.                 12a cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         2962, 2862, 2856, 1667,                                                       1613, 1567, 1514, 1397         13a cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         (COOH).sub.2                                                                          140° C.                 14a cyclohexyl                                                                             H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         --      2957, 2929, 2854, 1634,                                                       1512, 1449                     15a cyclohexyl                                                                             H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         HCl     105° C.                 16a cyclohexyl                                                                             H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         resin                          17a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         --      3277, 3179, 2960, 2931,                                                       2854, 1647, 1626               18a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         HI      128° C.                 19a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                          20a cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         --                                     21a cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         HI                                     22a cyclohexyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                          23a cyclohexyl                                                                             H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         --                                     24a cyclohexyl                                                                             H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI                                     25a cyclohexyl                                                                             H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                          26a cyclohexyl                                                                             H   H    H  3-(4-tert.-butylphenyl)-                                                                    HI      80° C.                                           2-methylpropyl                                       27a cyclohexyl                                                                             H   H    H  4-(2,3-dimethylbut-                                                                         HI      >200° C.                                         2-yl)-benzyl                                         28a cyclohexyl                                                                             H   H    H  n-tridecyl    HI      3283, 3252, 3181, 2926,                                                       2854,                                                                         1646, 1631, 1466, 1452,                                                       1369                           29a cyclohexyl                                                                             H   H    H  6,10-dimethylundec-2-yl                                                                     HI      3268, 3185, 2928, 2855,                                                       1667, 1646, 1624, 1451         30a cyclohexyl                                                                             H   H    H  3-(4-tert.-butylphenyl)-                                                                    HCl     169° C.                                          2-methylpropyl                                       31a cyclohexyl                                                                             H   H    H  3-(4-tert.-butylphenyl)-                                                                    1/2(COOH).sub.2                                                                       110° C.                                          2-methylpropyl                                       32a cyclohexyl                                                                             H   H    H  3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                         3020, 2959, 2931, 2857,                                 2-methylpropyl        1648, 1558, 1403, 1363         33a cyclohexyl                                                                             H   n-butyl                                                                            H  benzyl        CH.sub.3 COOH                                                                         2932, 2856, 1625,                                                             1596, 1569, 1496, 1452,                                                       1399, 1377, 1253               34a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         --      145° C.                 35a cyclopentyl                                                                            H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         --                                     36a cyclopentyl                                                                            H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      145° C.                 37a cyclooctyl                                                                             H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      82° C.                  38a cyclooctyl                                                                             H   H    CH.sub.3                                                                         4-tert.-butylbenzyl                                                                         --                                     39a cyclododecyl                                                                           H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      124° C.                 40a cyclododecyl                                                                           H   H    H  4-tert.-butylbenzyl                                                                         HI      170° C.                 41a 3-methyl-                                                                              H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      150° C.                     cyclohexyl                                                                42a 4-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      220° C.                     cyclohexyl                                                                43a 4-tert.-butyl-                                                                         H   H    H  4-tert.-butylbenzyl                                                                         HI      200° C.                     cyclohexyl                                                                44a 4-tert.-butyl-                                                                         H   H    H  4-tert.-butyloxybenzyl                                                                      HI      206° C.                     cyclohexyl                                                                45a 4-isopropyl-                                                                           H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      2959, 2933, 2867,                  cyclohexyl                                 1634, 1513, 1366               46a 4-isopropyl-                                                                           H   H    H  4-tert.-butyloxybenzyl                                                                      HI                                         cyclohexyl                                                                47a 3,3-dimethyl-                                                                          H   H    H  4-tert.-butylbenzyl                                                                         HI      180° C.                     cyclohexyl                                                                48a 3,3-dimethyl-                                                                          H   H    H  4-tert.-butyloxybenzyl                                                                      --                                         cyclohexyl                                                                49a 3,3-dimethyl-                                                                          H   H    H  3-(4-tert-butylphenyl)-                                                                     HI      110° C.                     cyclohexyl           2-methyl-propyl                                      50a 3-trifluoro-                                                                           H   H    H  4-tert.-butylbenzyl                                                                         HI      90° C.                      methylcyclohexyl                                                          51a 3-trifluoro-                                                                           H   H    H  4-tert.-butyloxybenzyl                                                                      --                                         methylcyclohexyl                                                          52a 3-trifluoro-                                                                           H   H    H  3-(4-tert-butylphenyl)-                                                                     HI      95° C.                      methylcyclohexyl     2-methyl-propyl                                      53a 3,3-dimethyl-                                                                          H   H    H  4-tert.-butylbenzyl                                                                         HCl     >200° C.                    cyclohexyl                                                                54a 3,3-dimethyl-                                                                          H   H    H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         120° C.                     cyclohexyl                                                                55a 3,3-dimethyl-                                                                          H   H    H  4-tert.-butylbenzyl                                                                         (COOH).sub.2                                                                          155° C.                     cyclohexyl                                                                56a 4-tert.-butyl-                                                                         H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         2959, 2866, 1629, 1572,            cyclohexyl                                 1515, 1393, 1366               57a 4-tert.-butyl-                                                                         H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         HCl     110° C.                     cyclohexyl                                                                58a 3-methyl-                                                                              H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         HCl     75° C.                      cyclohexyl                                                                59a 3-methyl-                                                                              H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         2957, 2929, 2869, 1628,            cyclohexyl                                 1571, 1515, 1458, 1394,                                                       1367, 1268                     60a 3-methyl-                                                                              H   H    H  4-tert.-butylbenzyl                                                                         HI      100° C.                     cyclohexyl                                                                61a 2-methyl-                                                                              H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      102° C.                     cyclohexyl                                                                62a cyclohexyl                                                                             H   iso- H  4-tert.-butylbenzyl                                                                         HCl     135° C.                                  propyl                                                       63a cyclohexyl                                                                             H   but- H  4-tert.-butylbenzyl                                                                         HCl     105° C.                                  2-yl                                                         64a cyclohexyl                                                                             H   H    H  4-chlorobenzyl                                                                              HI      80° C.                  65a cyclohexyl                                                                             H   H    H  2,4-dichlorobenzyl                                                                          HI      3270, 3274, 2931, 1648,                                                       1624, 1589, 1563, 1544         66a cyclohexyl                                                                             H   H    H  4-cyanaboenzyl                                                                              --                                     67a cyclohexyl                                                                             H   H    H  4-trifluoromethylbenzyl                                                                     --                                     68a cyclohexyl                                                                             H   H    H  1-phenyl-ethyl                                                                              --                                     69a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 3-(4-tert.-butyl-                                                          HI      195° C.                                       phenyl)-pyrrolidinyl                                    70a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                           HI      135° C.                                       2-yl)-pyrrolidinyl                                      71a 3,3-dimethyl-                                                                          H   H    R.sup.3 + R.sup.4 =  3-(4-tert.-butyl-                                                         HI      170° C.                     cyclohexyl        phenyl)-pyrrolidinyl                                    72a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 4-isopropyl-                                                               HI      169° C.                                       piperidinyl                                             73a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                           HI      110° C.                                       2-yl)-pyrrolidinyl                                      74a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                           CH.sub.3 COOH                                                                         3272, 3165, 2931, 2859,                              2-yl)-pyrrolidinyl       1660, 1617, 1557, 1468,                                                       1452, 1383                     75a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 3-(6-methylhept-                                                           (COOH).sub.2                                                                          3200, 2932, 2859, 1738,                              2-yl)-pyrrolidinyl       1647, 1620, 1553, 1467,                                                       1452, 1205                     76a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 3-(2,4,4-trimethyl-                                                        HI      175° C.                                       pentyl)-pyrrolidinyl                                    77a 4-tert.-butyl-                                                                         H   H    H  3-(4-tert.-butylphenyl)-                                                                    --                                         cyclohexyl           2-methylpropyl                                       78a 4-(2,4,4-tri-                                                                          H   H    H  4-tert.-butylbenzyl                                                                         HI      100°  C.                    methylhex-2-yl)-                                                              cyclohexyl                                                                79a 4-(2,4,4-tri-                                                                          H   H    H  3-(4-tert-butylphenyl)-                                                                     --                                         methylhex-2-yl)-     2-methylpropyl                                           cyclohexyl                                                                80a 4-ethoxy-                                                                              H   H    H  4-tert.-butylbenzyl                                                                         --                                         cyclohexyl                                                                81a 4-hydroxyethyl-                                                                        H   H    H  4-tert.-butylbenzyl                                                                         --                                         cyclohexyl                                                                82a 4-chlorocyclo-                                                                         H   H    H  4-tert.-butylbenzyl                                                                         --                                         hexyl                                                                     83a 4-tert.-buto-                                                                          H   H    H  4-tert.-butylbenzyl                                                                         --                                         oxycyclohexyl                                                             84a 4-tert.-buto-                                                                          H   H    H  4-tert.-butyloxybenzyl                                                                      --                                         oxycyclohexyl                                                             85a 3,3,5-tri-                                                                             H   H    H  4-tert.-butyloxybenzyl                                                                      --                                         methylcyclohexyl                                                          86a 3,3,5-tri-                                                                             H   H    H  4-tert.-butyloxybenzyl                                                                      --                                         methylcyclohexyl                                                          87a 4-chloroethyl-                                                                         H   H    H  4-tert.-butyloxybenzyl                                                                      --                                         cyclohexyl                                                                88a 4-chloroethyl-                                                                         H   H    H  4-tert.-butyloxybenzyl                                                                      --                                         cyclohexyl                                                                89a cyclohexyl                                                                             H   H    H  4-hydroxybenzyl                                                                             --                                     90a cyclohexyl                                                                             H   H    H  4-trichloromethylbenzyl                                                                     --                                     91a cyclohexyl                                                                             H   H    H  4-methoxybenzyl                                                                             HI      48° C.                  92a cyclohexyl                                                                             H   H    H  2-(4-methoxyphenyl)ethyl                                                                    HI      3249, 3179, 2932, 1647,                                                       1629, 1513, 1247               93a cyclohexyl                                                                             H   H    H  C.sub.13 H.sub.27 (isomer mixture)                                                          --                                     94a cyclohexyl                                                                             H   H    H  cyclohexylmethyl                                                                            --                                     95a cyclohexyl                                                                             H   H    H  2,2-dimethylpropyl                                                                          --                                     96a cyclohexyl                                                                             H   H    H  n-hexyl       --                                     97a cyclohexyl                                                                             H   H    H  n-octyl       HI      3285, 3250, 3181, 2929,                                                       2855, 1647, 1631, 1602         98a cyclohexyl                                                                             H   H    H  3-methyl-butyl                                                                              --                                     99a cyclohexyl                                                                             H   H    H  phenethyl     --                                    100a cyclohexyl                                                                             H   H    H  2-ethylhexyl  HI      3284, 3252, 3181, 2958,                                                       2930, 2857, 1647, 1630        101a cyclohexyl                                                                             H   H    H  6-ethyl-4-oxadecyl                                                                          --                                    102a cyclohexyl                                                                             H   H    H  4-tert.-butyl-                                                                              --                                                              phenylpropyl                                        103a cyclohexyl                                                                             H   H    H  3-tert.-butylbenzyl                                                                         --                                    104a 2-hydroxy-1,1-                                                                         H   H    H  4-tert.-butylbenzyl                                                                         --                                         dimethyl-ethyl-                                                               cyclohexyl                                                               105a cyclohexyl                                                                             H   H    H  4-isopropylbenzyl                                                                           --                                    106a cyclohexyl                                                                             H   H    H  4-(2,4,4-trimethyl-                                                                         --                                                              pentyl)benzyl                                       107a 4-tert.-butyl-                                                                         H   H    H  4-tert.-amylbenzyl                                                                          --                                         cyclohexyl                                                               108a 1-methoxy-1-                                                                           H   H    H  4-tert.-butoxybenzyl                                                                        --                                         methylethyl-                                                                  cyclohexyl                                                               109a cyclohexyl                                                                             H   H    H  4-(1-methoxy-1-methyl-                                                                      --                                                              ethyl)benzyl                                        110a cyclohexyl                                                                             H   H    H  4(1-hydroxy-1-methyl-                                                                       --                                                              ethyl)benzyl                                        111a cyclohexyl                                                                             H   H    H  4-isopropenyl-benzyl                                                                        --                                    112a cyclohexyl                                                                             H   H    H  4-n-butoxy-benzyl                                                                           --                                    113a 4-tert.-amyl-                                                                          H   H    H  4-tert.-butylbenzyl                                                                         --                                         cyclohexyl                                                               114a cyclohexyl                                                                             H   H    H  2-methyl-4-tert.-                                                                           --                                                              butyl-benzyl                                        115a cyclohexyl                                                                             H   H    H  3,5,5-trimethylhexyl                                                                        --                                    116a cyclohexyl                                                                             H   H    H  6,10-14-trimethyl-                                                                          HI      3273, 3183, 2927, 2855,                                 pentadec-2-yl         1647, 1624, 1597, 1533        117a cyclohexyl                                                                             H   H    H  4-(4-tert.-butoxy-                                                                          HI      2974, 2930, 1608, 1450,                                 phenyl)-but-2-yl      1365, 1161                    118a cyclohexyl                                                                             H   H    H  2-(4-tert.-butyl-                                                                           HI      3291, 3220, 3173, 2965,                                 phenyl)-ethyl         2952, 2931, 1640, 1633        119a cyclohexyl                                                                             H   H    H  3-chlorobenzyl                                                                              HI      3249, 3178, 2931, 2854,                                                       1647, 1625, 1597, 1576        120a cyclohexyl                                                                             H   H    H  5-methyl-oct-2-yl                                                                           --                                    121a cyclohexyl                                                                             H   H    H  3,4,5-trimethoxybenzyl                                                                      --                                    122a cyclohexyl                                                                             H   H    H  4-methoxybenzyl                                                                             --                                    123a 4-(1-methoxy-                                                                          H   H    H  4-tert.-butylcyclohexyl                                                                     --                                         1-methyl)ethyl-                                                               cyclohexyl                                                               124a cyclohexyl                                                                             H   H    H  3-(4-tert.-butylphenyl)-                                                                    --      2958, 2928, 2854, 1615,                                 2-methylpropyl        1570, 1510, 1450, 1363        125a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4  = 3-(6-methylhept-2-yl)-                                                    --      2952, 2926, 2853, 1591,                              pyrrolidinyl             1542, 1518, 1449, 1364        126a cyclohexyl                                                                             H   H    H  benzyl        HI      134° C.                127a cyclohexyl                                                                             H   H    H  n-undecyl     HI      3283, 3251, 3182, 2927,                                                       2854, 1647, 1630, 1452        128a cyclohexyl                                                                             H   H    H  n-tetradecyl  HI      3251, 3180, 2925,                                                             2854, 1648, 1631              129a cyclohexyl                                                                             H   H    H  oct-2-yl      HI      3275, 3182, 2929, 2855,                                                       1647, 1624, 1600, 1553        130a cyclohexyl                                                                             H   H    H  4-phenylbutyl HI      3277, 3182, 3084, 2932,                                                       2856, 1648, 1630, 1452        131a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 4-(2,6-dimethyl)-                                                          HI      150° C.                                       morpholinyl                                            132a cyclohexyl                                                                             H   H    H  n-dodecanyl   HI      3248, 3180, 2924,                                                             2853, 1647, 1631              133a cyclohexyl                                                                             H   H    H  2,3-dimethoxy-benzyl                                                                        HI      178° C.                134a cyclohexyl                                                                             H   H    H  4-bromobenzyl HI      3369, 3312, 3246, 3188,                                                       2931, 1651, 1624, 1489        135a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 3-methyl-4-(4-tert.-                                                       HI      128° C.                                       butylphenyl)-pyrrolidinyl                              136a cyclohexyl                                                                             H   H    H  3,4-dichlorobenzyl                                                                          HI      3281, 3179, 2930,                                                             1648, 1624, 1470              137a cyclohexyl                                                                             H   H    H  2-chlorobenzyl                                                                              HI      3248, 3174, 2930, 2854,                                                       1646, 1625, 1444              138a cyclohexyl                                                                             H   H    R.sup.3 + R.sup.4 = 4-(4-tert-butylphenyl)-                                                    HI      205° C.                                       piperidinyl                                            139a cyclohexyl                                                                             H   H    CH.sub.3                                                                         2,5,7,7-tetramethyl-                                                                        HI      3300, 3194, 3166, 2950,                                 octyl                 2932, 1638, 1616, 1544        140a cyclohexyl                                                                             H   H    H  4-(1,1,3,3-tetramethyl-                                                                     HI      75° C.                                           butyl)-benzyl                                       141a cyclohexyl                                                                             H   H    H  n-pentyl      HI      3281, 3250, 3182, 2930,                                                       2856, 1646, 1629, 1600        142a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         H.sub.3 BO.sub.3                                                                      72° C.                 143a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         acetyl  3282, 3184, 2932, 2855,                                               acetonate                                                                             1646, 1629, 1451              144a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         o-hydroxy-                                                                            52° C.                                                         phenol                                145a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         C.sub.6 H.sub.5 COOH                                                                  70° C.                 146a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         CCl.sub.3 COOH                                                                        3317, 3197, 2935, 2859.                                                       1659, 1633, 1324, 832         147a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         3,4,5-  125° C.                                                        (OH).sub.3                                                                    C.sub.6 H.sub.5 COOH                  148a cyclohexyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         H.sub.2 CO.sub.3                                                                      87° C.                 149a cyclohexyl                                                                             H   H    H  4-(1,1,2-trimethyl-                                                                         HCl     180° C.                                          propyl)-benzyl                                      150a cyclohexyl                                                                             H   H    H  4-(1,1,2-trimethyl-                                                                         CH.sub.3 COOH                                                                         250° C.                                          propyl)-benzyl                                      151a cyclohexyl                                                                             H   H    H  4-(1,1,3-trimethyl-                                                                         C.sub.2 H.sub.2 O.sub.4                                                               75° C.                                           propyl)-benzyl                                      152a cyclohexyl                                                                             H   H    H  n-tridecyl    HCl     120° C.                153a cyclohexyl                                                                             H   H    H  n-tridecyl    CH.sub.3 COOH                                                                         3173, 2925, 2853, 1651,                                                       1569, 1465, 1452, 1404        154a cyclohexyl                                                                             H   H    H  n-tridecyl    C.sub.2 H.sub.2 O.sub.4                                                               3299, 3191, 2925, 2853,                                                       1636, 1465, 1453, 1218,                                                       720                           155a cyclohexyl                                                                             H   H    H  6,10-dimethyl-undec-                                                                        HCl     120° C.                                          2-yl                                                156a cyclohexyl                                                                             H   H    H  6,10-dimethyl-undec-                                                                        CH.sub.3 COOH                                                                         3272, 3175, 2928, 2856,                                 2-yl                  1571, 1450, 1402, 1014        157a cyclohexyl                                                                             H   H    H  6,10-dimethyl-undec-                                                                        C.sub.2 H.sub.2 O.sub.4                                                               3272, 3189, 2929, 1628,                                 2-yl                  1603, 1403, 1191, 720         158a 4-tert.-butyl-                                                                         H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         --      2958, 2862, 1636                   cyclohexyl                                 1512, 1365                    159a 4-tert.-butyl-                                                                         H   H    R.sup.3 + R.sup.4 = 2-methyl-3-(4-tert.-                                                       HI      245° C.                     cyclohexyl        butylphenyl)-pyrrolidinyl                              160a 4-tert.-butyl                                                                          H   H    H  3-(morpholin-4-yl)-                                                                         HI      3276, 3186, 2947, 2860,            cyclohexyl           prop-1-yl             1630, 1450, 1141, 1116        161a 4-tert.-butyl                                                                          H   H    CH.sub.3                                                                         2,5,7,7-tetramethyl-                                                                        HI      202° C.                     cylcohexyl           octyl                                               162a 4-tert.-butyl-                                                                         H   H    H  2,4-dichlorobenzyl                                                                          HI      163° C.                     cyclohexyl                                                               163a 4-tert.-butyl-                                                                         H   H    H  4-tert.-butylbenzyl                                                                         HCl     162° C.                     cyclohexyl                                                               164a 4-tert.-butyl-                                                                         H   H    H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         170° C.                     cyclohexyl                                                               165a 4-tert.-butyl-                                                                         H   H    H  4-tert.-butylbenzyl                                                                         C.sub.2 H.sub.2 O.sub.4                                                               102° C.                     cyclohexyl                                                               166a 3-methyl-                                                                              H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         --      2955, 2925, 2867,                  cyclohexyl                                 1636, 1512, 1458              167a 2-methyl-                                                                              H   H    H  4-tert.-butylbenzyl                                                                         HI      144° C.                     cyclohexyl                                                               168a 3-methyl-                                                                              H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HCl     142° C.                     cyclohexyl                                                               169a 3-methyl-                                                                              H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         102° C.                     cyclohexyl                                                               170a 3-methyl-                                                                              H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         C.sub.2 H.sub.2 O.sub.4                                                               173° C.                     cyclohexyl                                                               171a 3-methyl-                                                                              H   H    H  6,10-dimethylundec-                                                                         CH.sub.3 COOH                                                                         3179, 3092, 2951, 2927,            cyclohexyl           2-yl                  2867, 1644, 1557, 1460        172a 2,6-dimethyl-                                                                          H   H    H  3(4-tert.-butylphenyl)-                                                                     HI      3188, 2960, 2929,                  cyclohexyl           2-methylpropyl        2871, 1569, 1463              173a 4-hydroxy                                                                              H   H    H  4-tert.-butylbenzyl                                                                         HI      100°  C.                    cyclohexyl                                                               174a 3-methyl-                                                                              H   H    H  4-tert.-butylbenzyl                                                                         HCl     130° C.                     cyclohexyl                                                               175a 3-methyl-                                                                              H   H    H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         105° C.                     cyclohexyl                                                               176a 3-methyl-                                                                              H   H    H  4-tert.-butylbenzyl                                                                         C.sub.2 H.sub.2 O.sub.4                                                               95° C.                      cyclohexyl                                                               177a 3,3-dimethyl-                                                                          H   H    H  3-(4-tert.-butylphenyl)-                                                                    HCl     100° C.                     cyclohexyl           2-methylpropyl                                      178a 3,3-dimethyl-                                                                          H   H    H  3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                         100° C.                     cyclohexyl           2-methylpropyl                                      179a 3,3-dimethyl-                                                                          H   H    H  3-(4-tert.-butylphenyl)-                                                                    C.sub.2 H.sub.2 O.sub.4                                                               112° C.                     cyclohexyl           2-methylpropyl                                      180a cyclopentyl                                                                            H   H    H  4-tert.-butylbenzyl                                                                         HI      88° C.                 181a cyclopentyl                                                                            H   H    H  3-(4-tert.-butylbenzyl)-                                                                    CH.sub.3 COOH                                                                         3304, 3184, 3089, 2962,                                 2-methylpropyl        2871, 1650, 1561, 1401        182a cyclopentyl                                                                            H   H    H  6,10-dimethylundec-2-yl                                                                     CH.sub.3 COOH                                                                         3175, 2955, 2927, 2869,                                                       1646, 1560, 1400              183a cycloheptyl                                                                            H   H    H  4-tert.-butylbenzyl                                                                         HI      3253, 3180, 2960, 2927,                                                       2857, 1645, 1626, 1460        184a cyclooctyl                                                                             H   H    H  4-tert.-butylbenzyl                                                                         HI      90° C.                 185a cyclooctyl                                                                             H   H    H  3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                         3186, 3091, 2961, 2924,                                 2-methylpropyl        2868, 1649, 1561, 1404        186a cyclooctyl                                                                             H   H    H  6,10-dimethyl-undec-                                                                        CH.sub.3 COOH                                                                         2951, 2925, 2867, 1643,                                 2-yl                  1559, 1465, 1400              187a cyclohexyl                                                                             H   iso- H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         72° C.                                   propyl                                                      188a cyclohexyl                                                                             H   but- H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         80° C.                                   2-yl                                                         1b  p-tert.butyl-                                                                          H   CH.sub.3                                                                           H  3-(4-tert.butylphenyl)-                                                                     HCl     125° C.                     benzyl               2-methylpropyl                                       2b  p-tert.-butyl-                                                                         H   CH.sub.3                                                                           R.sup.3 + R.sup.4 = 4-tert.butyl-                                                              HI      155° C.                     benzyl            piperidinyl                                             3b  p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         --      2963, 2904, 2867, 1863,            benzyl                                     1637, 1513, 1476, 1464         4b  p-tert.-btuyl-                                                                         H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HCl     125° C.                     benzyl                                                                    5b  p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  4-tert.butylbenzyl                                                                          CH.sub.3 COOH                                                                         2963, 2905, 1638, 1568,            benzyl                                     1514, 1477, 1393, 1365         6b  p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  cyclohexylmethyl                                                                            HI      186° C.                     benzyl                                                                    7b  p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3,5,5-trimethylhexyl                                                                        HI      165° C.                     benzyl                                                                    8b  benzyl   H   n-butyl                                                                            H  3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                         2958, 2928, 2869, 1639,                                 2-methylpropyl        1510, 1495, 1453, 1362         9b  p-tert.-butyl-                                                                         H   n-butyl                                                                            R.sup.3 + R.sup.4 = cis-2,6-dimethyl-                                                          CH.sub.3 COOH                                                                         2963, 2935, 2872, 1627,            benzyl            morpholin-4-yl           1590, 1269, 1087               10b p-tert.-butyl-                                                                         H   n-butyl                                                                            R.sup.3 + R.sup.4 = cis-2,6-dimethyl-                                                          HCl     60° C.                      benzyl            morpholin-4-yl                                          11b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  2,2-dimethylpropyl                                                                          HCl     88° C.                      benzyl                                                                    12b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  2,2-dimethylpropyl                                                                          CH.sub.3 COOH                                                                         2962, 2872, 1630, 1574,            benzyl                                     1394, 1366                     13b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         CH.sub.3 COOH                                                                         2962, 2906, 1634, 1570,            benzyl                                     1394                           14b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         HCl     102° C.                     benzyl                                                                    15b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  3-(4-tert.-butylphenyl)-                                                                    HCl     95 to 100° C.               benzyl               2-methylpropyl                                       16b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                         2962, 2933, 1633, 1571,            benzyl               2-methylpropyl        1394, 1364                     17b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  n-pentyl      --                                         benzyl                                                                    18b p-tert.-butyl-                                                                         H   H    H  n-hexyl       HI      156° C.                     benzyl                                                                    19b p-tert.-butyl-                                                                         H   H    H  n-heptyl      HI      135° C.                     benzyl                                                                    20b p-tert.-butyl-                                                                         H   H    H  n-octyl       HI      113° C.                     benzyl                                                                    21b p-tert.-butyl-                                                                         H   H    H  n-nonyl       HI      3247, 3179, 2956, 2924,            benzyl                                     2854, 1649, 1629, 1465         22b p-tert.-butyl-                                                                         H   H    H  n-decyl       HI      3248, 3179, 2957, 2925,            benzyl                                     2855, 1649, 1630, 1466         23b p-tert.-butyl-                                                                         H   H    H  n-dodecyl     HI      3247, 3180, 2957, 2924,            benzyl                                     2854, 1649, 1630, 1466         24b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-hexyl       HI      177° C.                     benzyl                                                                    25b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-octyl       HI      122° C.                     benzyl                                                                    26b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-decyl       HI      85° C.                      benzyl                                                                    27b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-dodecyl     HI      96°  C.                     benzyl                                                                    28b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  2,2-dimethylpropyl                                                                          HI      165° C.                     benzyl                                                                    29b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-methyl-butyl                                                                              HI      137° C.                     benzyl                                                                    30b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           R.sup.3 + R.sup.4 = piperidinyl                                                                HI      82° C.                      benzyl                                                                    31b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  phenethyl     HI      87° C.                      benzyl                                                                    32b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  benzyl        HI      124° C.                     benzyl                                                                    33b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-(4-tert.-butylphenyl)-                                                                    HI      165° C.                     benzyl               2-methylpropyl                                       34b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  2-ethyl-hexyl HI      65° C.                      benzyl                                                                    35b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-tridecyl    HI      105° C.                     benzyl                                                                    36b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  4-methoxy-phenethyl                                                                         HI      137° C.                     benzyl                                                                    37b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  6-ethyl-4-oxa-decyl                                                                         HI      3218, 2959, 2929, 2870,            benzyl                                     1623, 1462, 1380, 1109         38b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  4-phenyl-but-2-yl                                                                           HI      102° C.                     benzyl                                                                    39b p-tert.-butoxy-                                                                        H   H    H  4-tert.-butyl-cyclo-                                                                        HI      192° C.                     benzyl               hexylmethyl                                          40b p-tert.-butyl-                                                                         H   H    H  4-tert.-butyl-cyclo-                                                                        HI      192° C.                     benzyl               hexylmethyl                                          41b p-tert.-butyl-                                                                         H   H    H  1-phenyl-ethyl                                                                              HI      70° C.                      benzyl                                                                    42b p-tert.-butyl-                                                                         H   H    H  4-phenyl-but-2-yl                                                                           HI      75° C.                      benzyl                                                                    43b p-tert.-butyl-                                                                         H   H    H  3-diethylaminopropyl                                                                        HI      3243, 3179, 2964, 2870,            benzyl                                     2822, 1629, 1465, 1366         44b p-tert.-butyl-                                                                         H   H    H  4-methoxy-phenethyl                                                                         HI      3303, 3185, 3164, 1643,            benzyl                                     1632, 1595, 1512, 1242         45b p-tert.-butyl-                                                                         H   H    H  phenethyl     HI      130° C.                     benzyl                                                                    46b p-tert.-butyl-                                                                         H   H    H  2-ethylhexyl  HI      3251, 3181, 2960, 2929,            benzyl                                     2872, 1649, 1630, 1464         47b p-tert.-butyl-                                                                         H   H    H  benzyl        HI      58° C.                      benzyl                                                                    48b p-tert.-butyl-                                                                         H   H    R.sup.3 + R.sup.4 = 4-tert.-butyl-                                                             HI      183° C.                     benzyl            piperidinyl                                             49b p-tert.-butyl-                                                                         H   H    H  4-tert.-butylbenzyl                                                                         HI      182°  C.                    benzyl                                                                    50b p-tert.-butyl-                                                                         H   H    H  3-(4-tert.-butylphenyl)-                                                                    HI      152° C.                     benzyl               2-methylpropyl                                       51b p-tert.-butyl-                                                                         H   H    H  tridecyl      HI      89° C.                      benzyl                                                                    52b p-tert.-butyl-                                                                         H   H    H  6-ethyl-4-oxa-decyl                                                                         HI      100° C.                     benzyl                                                                    53b p-tert.-butyl-                                                                         H   H    R.sup.3 + R.sup.4 = piperidinyl                                                                HI      72° C.                      benzyl                                                                    54b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  4-tert.-butyl-cyclo-                                                                        HI      125° C.                     benzyl               hexylmethyl                                          55b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-diethylaminopropyl                                                                        HI      3210, 3102, 2964, 2870,            benzyl                                     1620, 1458, 1383, 1364         56b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  1-phenyl-ethyl                                                                              HI      163° C.                     benzyl                                                                    57b p-(1,1-dimethyl-                                                                       H   H    H  n-hexyl       --                                         ethyl)-benzyl                                                             58b p-(1,1-dimethyl-                                                                       H   H    H  n-heptyl      --                                         ethyl)-benzyl                                                             59b p-(1,1-dimethyl-                                                                       H   H    H  n-octyl       --                                         ethyl)-benzyl                                                             60b p-(1,1-dimethyl-                                                                       H   H    H  n-nonyl       --                                         ethyl)-benzyl                                                             61b p-(1,1-dimethyl-                                                                       H   H    H  tert.-butylbenzyl                                                                           --                                         ethyl)-benzyl                                                             62b p-(1,1-dimethyl-                                                                       H   H    H  3-methylbutyl --                                         ethyl)-benzyl                                                             63b p-(1,1-dimethyl-                                                                       H   H    H  3-(4-tert.-butylphenyl)-                                                                    --                                         ethyl)-benzyl        2-methylpropyl                                       64b p-tert.-butoxy-                                                                        H   H    H  n-hexyl       --                                         benzyl                                                                    65b p-tert.-butoxy-                                                                        H   H    H  n-heptyl      --                                         benzyl                                                                    66b p-tert.-butoxy-                                                                        H   H    H  n-octyl       --                                         benzyl                                                                    67b p-tert.-butoxy-                                                                        H   H    H  n-nonyl       --                                         benzyl                                                                    68b p-tert.-butoxy-                                                                        H   H    H  n-decyl       --                                         benzyl                                                                    69b p-tert.-butoxy-                                                                        H   H    H  3-methylbutyl --                                         benzyl                                                                    70b p-tert.-butoxy-                                                                        H   H    H  tert.-butylbenzyl                                                                           --                                         benzyl                                                                    71b p-tert.-butoxy-                                                                        H   H    H  tert.-butoxybenzyl                                                                          --                                         benzyl                                                                    72b p-tert.-butoxy-                                                                        H   H    H  n-octyl       --                                         benzyl                                                                    73b p-(1,1,2-tri-                                                                          H   H    H  n-hexyl       --                                         methylpropyl)-                                                                benzyl                                                                    74b p-(1,1,2-tri-                                                                          H   H    H  n-heptyl      --                                         methylpropyl)-                                                                benzyl                                                                    75b p-(1,1,2-tri-                                                                          H   H    H  n-octyl       --                                         methylpropyl)-                                                                benzyl                                                                    76b p-(1,1,2-tri-                                                                          H   H    H  n-nonyl       --                                         methylpropyl)-                                                                benzyl                                                                    77b p-(1,1,2-tri-                                                                          H   H    H  n-decyl       --                                         methylpropyl)-                                                                benzyl                                                                    78b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  cyclohexylmethyl                                                                            HCl     155° C.                     benzyl                                                                    79b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  cyclohexylmethyl                                                                            CH.sub.3 COOH                                                                         82° C.                      benzyl                                                                    80b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  cyclohexylmethyl                                                                            (COOH).sub.2                                                                          168° C.                     benzyl                                                                    81b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3,5,5-trimethylhexyl                                                                        (COOH).sub.2                                                                          180° C.                     benzyl                                                                    82b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3,5,5-trimethylhexyl                                                                        CH.sub.3 COOH                                                                         75° C.                      benzyl                                                                    83b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3,5,5-trimethylhexyl                                                                        HCl     107° C.                     benzyl                                                                    84b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-hexyl       HCl     105° C.                     benzyl                                                                    85b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-hexyl       CH.sub.3 COOH                                                                         110° C.                     benzyl                                                                    86b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-hexyl       (COOH).sub.2                                                                          185° C.                     benzyl                                                                    87b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-methylbutyl (COOH).sub.2                                                                          182° C.                     benzyl                                                                    88b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-methylbutyl CH.sub.3 COOH                                                                         72° C.                      benzyl                                                                    89b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-methylbutyl HCl     105° C.                     benzyl                                                                    90b p-tert.-butyl-                                                                         H   H    H  6-ethyl-4-oxa-decyl                                                                         HCl     oil, 3260, 3173, 2959,                                                        2930,                              benzyl                                     2871, 1655, 1637, 1464         91b p-tert.-butyl-                                                                         H   H    H  6-ethyl-4-oxa-decyl                                                                         CH.sub.3 COOH                                                                         oil, 2959, 2929, 2870,                                                        1653,                              benzyl                                     1560, 1515, 1403, 1110         92b p-tert.-butyl-                                                                         H   H    H  6-ethyl-4-oxa-decyl                                                                         (COOH).sub.2                                                                          oil, 3183, 2958, 2929,                                                        2870,                              benzyl                                     1633, 1462, 1220, 1109         93b p-tert.-butyl-                                                                         H   H    H  4-tert.-butoxybenzyl                                                                        (COOH).sub.2                                                                          118° C.                     benzyl                                                                    94b p-tert.-butyl-                                                                         H   H    H  4-tert.-butoxybenzyl                                                                        CH.sub.3 COOH                                                                         168° C.                     benzyl                                                                    95b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                         97° C.                      benzyl               2-methylpropyl                                       96b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-(4-tert.-butylphenyl)-                                                                    H.sub.3 BO.sub.3                                                                      149° C.                     benzyl               2-methylpropyl                                       97b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  3-(4-tert.-butylphenyl)-                                                                    --      2960, 2903, 2867, 1636,            benzyl               2-methylpropyl        1512, 1474, 1462, 1362         98b p-tert.-butyl                                                                          H   H    H  2-ethylhexyl  HCl     80° C.                      benzyl                                                                    99b p-tert.-butyl                                                                          H   H    H  2-ethylhexyl  CH.sub.3 COOH                                                                         2959, 2928, 2870, 1569,            benzyl                                     1462, 1402, 1363, 1269        100b p-tert.-butyl                                                                          H   H    R.sup.3 + R.sup.4 = 4-tert.-butyl-                                                             HCl     250° C.                     benzyl            piperidinyl                                            101b p-tert.-butyl                                                                          H   H    R.sup.3 + R.sup.4 = 4-tert.-butyl-                                                             CH.sub.3 COOH                              benzyl            piperidinyl                                            102b p-tert.-butyl                                                                          H   H    H  3-(4-tert.-butylphenyl)-                                                                    HCl     90° C.                      benzyl               2-methylpropyl                                      103b p-tert.-butyl                                                                          H   H    H  3-(4-tert.-butylphenyl)-                                                                    CH.sub.3 COOH                                                                         3278, 3198, 2961, 1635,            benzyl               2-methylpropyl        1606, 1561, 1516, 1409        104b p-tert.-butyl                                                                          H   H    H  4-hydroxybenzyl                                                                             HCl     3323, 3263, 3170, 2961,            benzyl                                     1651, 1614, 1513, 1267        105b p-tert.-butyl                                                                          H   H    H  4-hydroxybenzyl                                                                             CH.sub.3 COOH                                                                         3180, 3026, 2962, 1645,            benzyl                                     1614, 1554, 1462, 1409        106b p-tert.-butyl                                                                          H   H    CH.sub.3                                                                         2,5,7,7-tetramethyl-                                                                        HI      58° C.                      benzyl               octyl                                               107b p-tert.-butyl                                                                          H   CH.sub.3                                                                           H  4-tert.-butylbenzyl                                                                         HI      90° C.                      benzyl                                                                   108b p-tert.-butyl-                                                                         H   H    R.sup.3 + R.sup.4 = 3-(1,5-dimethylhexyl)-                                                     HJ      172° C.                     benzyl            pyrrolidinyl                                           109b p-tert.-butyl-                                                                         H   H    R.sup.3 + R.sup.4 = 3-(1,5-dimethylhexyl)-                                                     HCl     190°  C.                    benzyl            pyrrolidinyl                                           110b p-tert.-butyl-                                                                         H   H    R.sup.3 + R.sup.4 = 3-(1,5-dimethylhexyl)-                                                     CH.sub.3 COOH                                                                         2955, 2928, 2868, 1610,            benzyl            pyrrolidinyl             1573, 1465, 1448, 1402        111b p-tert.-butyl-                                                                         H   H    H  n-undecyl     HI      3249, 3181, 2956, 2924,            benzyl                                     2853, 1649, 1629, 1464        112b p-tert.-butyl-                                                                         H   H    H  6-hydroxyhexyl                                                                              HI      3287, 3198, 2932, 2859,            benzyl                                     1650, 1629, 1547, 1462        113b p-tert.-butyl-                                                                         H   H    H  2-(2-hydroxyethoxy)-                                                                        HI      3299, 3188, 2958, 2869,            benzyl               ethyl                 1651, 1631, 1122, 1065        114b p-tert.-butyl-                                                                         H   H    H  6-hydroxy-6-methyl-hept-                                                                    HI      3297, 3188, 2964, 2867,            benzyl               2-yl                  1626, 1602, 1556, 1462        115b p-tert.-butyl-                                                                         H   H    H  6,10-dimethyl-undec-                                                                        HI      3249, 3180, 2954, 2926,            benzyl               2-yl                  2867, 1646, 1626, 1462        116b p-tert.-butyl-                                                                         H   H    H  2,2-dimethylpropyl                                                                          HI      85° C.                      benzyl                                                                   117b p-tert.-butyl-                                                                         H   H    H  3-methylbutyl HI      122° C.                     benzyl                                                                   118b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-butyl       HI      135° C.                     benzyl                                                                   119b p-tert.-butyl-                                                                         H   CH.sub.3                                                                           H  n-pentyl      HI      147° C.                     benzyl                                                                   120b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  cis-2,6-dimethyl-morpholin-                                                                 --      2962, 2931, 2904, 2869,            benzyl               4-yl                  1637, 1375, 1144, 1086        121b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  2,2-dimethylpropyl                                                                          --      2956, 2904, 2867, 1649,            benzyl                                     1513, 1476, 1464, 1362        122b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  4-tert.-butylbenzyl                                                                         --      2959, 2931, 2904, 2868,            benzyl                                     1633, 1513, 1463, 1362        123b p-tert.-butyl-                                                                         H   n-butyl                                                                            H  3-(4-tert.-butyl-phenyl)-                                                                   --      2960, 2928, 2869, 1640,            benzyl               2-methylpropyl        1512, 1462, 1362, 1269        124b p-tert.-butyl-                                                                         H   H    H  n-butyl       HI      3248, 3182, 2959, 2932,            benzyl                                     2870, 1649, 1630, 1463        125b p-tert.-butyl-                                                                         H   H    H  n-pentyl      HI      120° C.                     benzyl                                                                   __________________________________________________________________________

USE EXAMPLES

The active ingredientsN-1-(4-tert-butylphenyl)-N-2-cyclohexyl-N-3-allylguanidine (A),N-1-(4-tert-butylphenyl)-N-2-cyclohexyl-N-3-(3-N,N-dimethylamino-n-propyl)-guanidine(B) andN-1-(4-tert-butylphenyl)-N-2-cyclohexyl-N-3-(4-tert-butylcyclohexyl)-guanidine(C) disclosed in DE-A 31 08 564 were used for comparison purposes.

EXAMPLE 1 Action on Pyrenophora teres

Barley seedlings of the "Igri" variety were sprayed to runoff at thetwo-leaf stage with aqueous suspensions consisting (dry basis) of 80% ofactive ingredient and 20% of emulsifier. After 24 hours the plants wereinoculated with a spore suspension of the fungus Pyrenophora teres, andset up for 48 hours in a high-humidity climatic cabinet at 18° C. Theplants were then cultivated for a further 5 days in the greenhouse at20° to 22° C. and a relative humidity of 70° C. The extent of fungusspread was then assessed.

The results show that active ingredients 1a, 5a, 7a, 11a, 13a, 27a, 28a,31a, 32a, 39a, 49a, 54a, 57a, 75a, 1b, 3b, 4b, 7b, 8b, 13b, 14b, 15b,16b, 18b, 20b, 22b, 23b, 25b, 26b, 34b, 37b, 52b and 54b, applied as0.05 wt % spray liquors, have a better fungicidal action (85%) thanprior art comparative ingredients A, B and C (55%).

EXAMPLE 2 Action on wheat mildew

Leaves of pot-grown wheat seedlings of the "Kanzler" variety weresprayed with 0.025% aqueous spray liquors containing (dry basis) 80% ofactive ingredient and 20% of emulsifier, and dusted, 24 hours after thesprayed-on liquor had dried, with spores of wheat mildew (Erysiphegraminis var. tritici). The plants were then set up in the greenhouse atfrom 20° to 22° C. and a relative humidity of 75 to 80%. The extent offungus spread was assessed after 7 days.

The results show that active ingredients 1a, 15a, 26a, 32a, 47a, 49a,56a, 69a, 70a, 2b, 6b, 9b, 11b, 12b, 13b, 29b, 31b, 34b, 35b, 36b, 38b,45b and 46b, applied as 0.025 wt % spray liquors, have a betterfungicidal action (85%) than prior art comparative ingredients B and C(60%).

We claim:
 1. A substituted quanidine of the formula I ##STR20## where Ais benzyl which is substituted in the para-position by C₁ -C₁₀ -alkyl,where the substituent may furthermore carry a hydroxyl or C₁ -C₆ -alkoxygroup;R¹, R² and R³ are each hydrogen or C₁ -C₄ -alkyl, and R⁴ is C₈-C₁₄ -alkyl which may be interrupted by oxygen, or is a C₅ -C₁₈ -alkenylgroup, a C₄ -C₁₈ -alkynyl group or a benzyl group, where these groupsmay carry up to three of the following substituents: hydroxyl, halogen,cyano, C₁ -C₇ -alkoxy or up to two amino, C₁ -C₄ -alkylamino or di-C₁-C₄ -alkylamino substituents, and the phenyl moiety of the phenylalkylgroup may additionally carry a phenoxy group or up to three C₂ -C₄-alkenyl groups, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl groups or C₁ -C₆ -alkylgroups which may be unsubstituted or partially or completed halogenated,or C₅ -C₆ -cycloalkyl-C₁ -C₈ -alkyl where the cycloalkyl ring may carryup to three C₁ -C₄ -alkyl groups or up to two hydroxyl ortrifluoromethyl groups; or together with the radical R³ and the nitrogenatom, may form a 5- or 6-membered heterocyclic ring which may be mono-to trisubstituted by C₁ -C₆ -alkyl, phenyl or C₁ -C₆ -alkylphenyl andmay be interrupted by an oxygen atom; and the plant-tolerated mineralacid salts I-HX and metal complexes of
 1. 2. A guanidine as set forth inclaim 1, where the substituents have the following meanings:A isp-tert-butyl-benzyl; R¹, R² and R³ are each hydrogen or C₁ -C₄ -alkyl;R⁴ is C₆ -C₁₄ -alkyl which may be interrupted by oxygen, or is C₅ -C₁₈-alkenyl, C₄ -C₁₈ -alkynyl or phenyl-C₁ -C₆ -alkyl, and these groups maycarry up to three of the following substituents: hydroxyl, halogen,cyano, C₁ -C₇ -alkoxy or up to two amino, C₁ -C₄ -alkylamino or di-(C₁-C₄)-alkylamino substituents, and where the phenyl moiety of thephenylalkyl group may additionally contain a phenoxy group or up tothree C₂ -C₄ -alkenyl, C₁ -C₄ -alkoxy-C₁ -C₄ -alkyl or C₁ -C₆ -alkylgroups which may be unsubstituted or partially or completelyhalogenated, or a C₅ -C₆ -cycloalkyl-C₁ -C₈ -alkyl group where thecycloalkyl ring may carry up to three C₁ -C₄ -alkyl groups or up to twohydroxyl or trifluoromethyl groups; or together with the radical R³ andthe nitrogen atom may form a 5- or 6-membered heretocyclic ring whichmay be mono-or disubstituted by C.sub. 1 -C₆ -alkyl, phenyl or C₁ -C₆-alkylphenyl and may be interrupted by an oxygen atom;and theplant-tolerated mineral acid salts I.HX and metal complexes of I.
 3. Afungicidal composition containing a fungicidally effective amount of atleast one guanidine of the formula I, or a plant-tolerated salt or metalcomplex thereof, as set forth in claim 1, and a liquid or solid carrier.4. A fungicidal composition containing a fungicidally effective amountof at least one guanidine of the formula I, or a plant-tolerated salt ormetal complex thereof, as set forth in claim 3, and a liquid or solidcarrier.
 5. A method for combating fungi, wherein a fungicidallyeffective amount of a substituted guanidine of the formula I, ##STR21##where: A is benzyl which is substituted in the para-position by C₁ -C₁₀-alkyl or C₁ -C₁₀ -alkoxy, where the substituent may furthermore carry ahydroxyl or C₁ -C₆ -alkoxy group;R¹, R² and R³ are each hydrogen or C₁-C₄ -alkyl, and R⁴ is C₆ -C₁₄ -alkyl which may be interrupted by oxygen,or is a C₅ -C₁₈ -alkenyl group, a C₄ -C₁₈ -alkynyl group or a phenyl-C₁-C₆ -alkyl group, where these groups may carry up to three of thefollowing substituents: hydroxyl, halogen, cyano, C₁ -C₇ -alkoxy or upto two amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino substituents,and the phenyl moiety of the phenylalkyl group may additionally carry aphenoxy group or up to three C₂ -C₄ -alkenyl groups, C₁ -C₄ -alkoxy-C₁-C₄ -alkyl groups or C₁ -C₆ -alkyl groups which may be unsubstituted orpartially or completely halogenated, or C₅ -C₆ -cycloalkyl-C₁ -C₈ -alkylwhere the cycloalkyl ring may carry up to three C₁ -C₄ -alkyl where thecycloalkyl ring may carry up to three C₁ -C₄ -alkyl groups or up to twohydroxyl or trifluoromethyl groups; or, together with the radical R³ andthe nitrogen atom, may form a 5- or 6-membered heterocyclic ring whichmay be mono- to trisubstituted by C₁ -C₆ -alkyl, phenyl or C₁ -C₆-alkyl-phenyl and may be interrupted by an oxygen atom; or theplant-tolerated mineral acid salts I.HX and metal complexes of I, isplaced in contact with fungi, or the plants or their habitat threatenedby fungus attack, or on the seed of the threatened plants.
 6. The HIacid salt compound of claim 1 wherein A is p-tert.-butyl-benzyl, R¹ isH, R² is H, R³ is H and R⁴ is 2-ethylhexyl.
 7. The method of claim 5wherein the compound of formula I is the HI acid salt, A isp-tert.-butyl-benzyl, R¹ is H, R² is H, R₃ is H and R⁴ is 2-ethylhexyl.8. The composition of claim 3 wherein the compound of formula I is theHI acid salt, A is p-tert.-butyl-benzyl, R¹ is H, R² is H, R³ is H andR⁴ is 2-ethylhexyl.